The photochemical reactions of α,β,γ,δ -unsaturated diazo compounds at low temperature

The α,β:γ,δ-unsaturated tosylhydrazone lithium salts (4) undergo photolysis at ?60°C to give vinylcyclopropenes (10) and [l,2]diazeto[l,4-a] pyrroles (11) and/or (12). The formation of (11, X=H) establishes the intermediacy of (8, X=H) in the formation of the 3$\text{H}$-1,2-diazepine (9). The diazoalkene (5, X=Me) showed opposite electrocyclisation periselectivity to its thermal cyclisation and gave (11, X=Me) $\text{via}$ (8, X=Me), rather than the pyrazoles (2) and (3).     

The polymerization of 1,4-pentadiene to [3.3.1]bicyclo-linked chains

1, 4-Pentadiene has been polymerized by Ziegler-Natta catalysts to give amorphous polymers which are up to 64 wt.-% soluble. The polymers all have residual unsaturation which is substantially less than one double bond per mer, some as low as 0.1 double bond per mer. The polymerizations proceed by an unusual double inter-, double intramolecular cyclopolymerization mechanism leading to the formation of [3.3.1] bicyclic repeat units. Some main-chain (internal) unsaturation as well as pendant-group (external) unsaturation is observed. The latter results from incompletely cyclized 1,4-pentadiene units. The former is due to some concurrent isomerization of 1,4- to 1,3 pentadiene, which then copolymerizes with the 1,4 diene. The extent of isomerization varied with the catalyst system used. The soluble polymer fractions were brittle for internal unsaturations of less than about 0.05 double bond per mer and were viscous for higher values. The insoluble fractions were brittle and are believed to be lightly crosslinked.     

Conformational analysis and electronic structure of acetanilide

The calculations of the electronic structure and conformational analysis of the acetanilide were carried out using the CNDO/2 method. The results show that the endo form is 1.2 Kcal/mole more stable than the exo form. The most stable conformation of the exo isomer corresponds to the dihedral angle of 90 ° between the phenyl and acetamide plane, whereas the minimum energy conformation of the endo isomer corresponds to the dihedral angle 50 °–60 °. A comparison of the calculated and experimental dipole moments suggests also the dihedral angle of 50 °–60 °. A comparison with experiment indicates that this molecular orbital method is good for conformational analysis and gives electronic structure which is compatible with spectroscopic measurement. The calculated conformational analysis and electronic structure of the acetanilide are in excellent agreement with experiments.We thank Professor J. P. Green for helpful discussions. This research was supported by a grant from the National Institute of Mental Health (MH-17489-01).     

Construction of orbital angular momentum eigenfunctions for many-particle systems by harmonic projection

Formulas are derived which allow the direct construction of total orbital angular momentum eigenfunctions for many-particle systems without the use of Clebsch–Gordan coefficients. One of the equations is closely analogous to Dirac' identity for the total spin operator. This equation describes the action of L² on a function of the particle coordinates in terms of a class operator of the symmetric group and a "contraction operator." A general projection operator for constructing symmetric eigenfunctions of L² is presented.     

Microstructural investigation of monoglyceride-water coagel systems by NMR and CryoSEM

Monoglyceride coagels consist of a network of plate-like crystals and are formed from a swollen gel state (alpha-gel). In order to resolve the transition mechanism, coagels were prepared with monoglycerides that differ in fatty acid composition (monomyristate and palmitate/stearate, respectively). Rheology provided information on kinetics of coagel formation and the strength of the resulting crystal network. From NMR measurements, the surface-to-volume ratio, tortuosity, and dimensionality of the network were obtained. These findings were in line with qualitative and quantitative structural information obtained from CryoSEM. As a model for the behaviour of non-monoglyceride species, the dynamics of (perdeuterated) palmitic acid was monitored in both alpha-gels and coagels. The experimental data support a two-stage mechanism. In the first stage, two-dimensional separation of D- and L-isomers in the monoglyceride bilayers of the alpha-gel occurs. This process depends primarily on lateral diffusion rate of the monoglycerides. Palmitic acid can be accommodated in the alpha-gel bilayer, but in the coagels it is separated into relative mobile and mechanically weak junction zones between the crystal plates. In the second stage of coagel formation, the crystal plates also grow in the third dimension. Both monoglyceride type and concentration determine the kinetics of this process.     

The structure of mammalian fatty acid synthase turned back to front

On page 1667 of this issue, Stuart Smith and colleagues [1] demonstrate that the animal fatty acid synthase is a head-to-head dimer rather than the head-to-tail dimer depicted in textbooks. This has important ramifications for the mechanisms of other multifunctional enzymes such as polyketide synthases [2].     

Chromatographic study of anionic complexes

Summary In this paper we have reported our results on the attempted separation of copper(II), nickel(II), cobalt(II) and iron(III) in mixtures by filter paper strip chromatography, using aqueous ethanol as solvent. The effect of the presence of varying concentrations of citrate ion as a complexing agent in the mixtures has been studied. The complexing agent has been added in the metal solution, and not in the solvent as usually done by previous workers.     

Self-repairing polymers: poly(dioxaborolane)s containing trigonal planar boron

The molecular weight of poly(dioxaborolane)s can be controlled during the polymerization reaction or through post-polymerization processing in such a manner that hydrolytic damage to these materials may be repaired, thereby regenerating the polymer.     

A comparison of two methods for the preparation of 3-Deazapurine ribonucleosides

The reaction of the trimethylsilyl derivative of 4,6-dichloroimidazo[4,5-c]pyridine with 2,3,5-tri-O-benzoyl- D -ribofuranosyl bromide gave four nucleosides-the α- and β-anomers of the 1-isomer and the α- and β-anomers of the 3-isomer (3.9:2.7:1.5:1). In contrast, the fusion reaction of 4,6-dichloroimidazo[4,5-c ]pyridine with 1,2,3,5-tetra-O-acetyl-β- D -ribofuranose gave a high yield of the 1-β-isomer, which was converted to the known 3-deazaadenosine (4-amino-l-β- D -ribofuranosylimidazo[4,5-c]pyridine).     

Localized orbitals in hydrogen bonded systems

The localized molecular orbitals for a variety of hydrogen bonded systems are obtained from their INDO and CNDO/2 wavefunctions. The bonding of these systems is qualitatively discussed in light of the localized orbitals.